CN114171738A - Graphite negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Graphite negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN114171738A
CN114171738A CN202010947255.4A CN202010947255A CN114171738A CN 114171738 A CN114171738 A CN 114171738A CN 202010947255 A CN202010947255 A CN 202010947255A CN 114171738 A CN114171738 A CN 114171738A
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graphite
filler
natural
natural graphite
core
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CN114171738B (en
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周海辉
潘修军
***
张殿臣
任建国
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BTR New Material Group Co Ltd
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BTR New Material Group Co Ltd
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Priority to CN202010947255.4A priority Critical patent/CN114171738B/en
Priority to US17/776,177 priority patent/US20220393171A1/en
Priority to JP2022518273A priority patent/JP2022551407A/en
Priority to KR1020227009317A priority patent/KR20220053610A/en
Priority to PCT/CN2021/117482 priority patent/WO2022052994A1/en
Priority to EP21866046.2A priority patent/EP4049971A4/en
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Abstract

The invention provides a graphite cathode material, a preparation method thereof and a lithium ion battery. The graphite cathode material comprises a natural graphite core, a carbon coating layer and a graphitized filling agent, and pores are formed in the natural graphite core; the graphitized filler is filled in the internal pores of the natural graphite core; and the graphitized filler also forms the carbon coating. The method comprises the following steps: mixing natural graphite with a filler, and crushing to obtain graphite powder; and graphitizing the graphite powder under a protective atmosphere to obtain the graphite cathode material. The preparation method provided by the invention simultaneously performs the spheroidization of the natural graphite, the mixed coating of the spherical graphite and the filler and the filling of the filler in the internal gap of the spherical graphite, reduces the turnover and residual loss of materials, and has simple process and high production efficiency.

Description

Graphite negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention belongs to the technical field of energy storage materials, relates to a negative electrode material, a preparation method thereof and a lithium ion battery, and particularly relates to a graphite negative electrode material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries have the advantages of high operating voltage, high capacity density, long cycle life, no memory effect, and the like, and thus have been widely used in 3C products, electric bicycles, energy storage systems, and particularly in electric vehicles in recent years. At present, the negative electrode material of the lithium ion battery in the market is mainly a carbon negative electrode material, and comprises soft carbon, hard carbon and a graphite material. The graphite material has the advantages of good conductivity, high crystallinity, lower lithium intercalation/deintercalation potential, higher reversible capacity, stable charge-discharge voltage platform and the like, and is the most mature lithium ion battery cathode material commercialized at present.
The graphite material is divided into two categories of natural graphite and artificial graphite, wherein the natural graphite is generally spherical natural graphite which has the defects of high anisotropy, poor electrolyte selectivity, poor circulation, high expansion rate and the like. The spherical natural graphite is obtained by spheroidizing and crushing crystalline flake graphite, a large number of gaps exist in the spherical natural graphite, even if the spherical natural graphite is coated and modified on the outer surface, in the circulation process, electrolyte can gradually permeate into the inner gaps to generate side reaction, an SEI film generated at the inner gaps is continuously broken and repaired, and organic molecules in the electrolyte are co-embedded, so that the interlayer structure of the graphite is stripped and damaged, the expansion rate is high, and the capacity is continuously attenuated. Therefore, improving the cycle performance and expansion rate of natural graphite has been the focus of research and development of natural graphite negative electrode materials.
Disclosure of Invention
Based on the above, the invention aims to provide a graphite negative electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the graphite cathode material provided by the invention can be used for preparing the natural graphite cathode material with a compact structure and no internal gap defect.
In a first aspect, the present invention provides a graphite anode material comprising:
a natural graphite core having pores therein;
the carbon coating layer is formed on the surface of the natural graphite core;
a graphitized filler filled in the internal pores of the natural graphite core; and the graphitizing filler also forms the carbon coating.
The filling agent is filled in the pore defects inside the graphite core of the graphite cathode material, the outer part of the graphite core is coated with the structure, the internal densification is realized, the internal defects of natural graphite are eliminated, the material expansion is small, the circulation is good, and the comprehensive performance is excellent. The problem of selectivity of the natural graphite and the electrolyte is solved, and the cycle performance of the natural graphite is improved.
In one embodiment, the graphite inner core has a median particle size of 8 to 25 μm.
In one embodiment, the filler in the graphitized filler comprises at least one of pitch and resin;
in one embodiment, the thickness of the carbon coating layer is 10nm to 100 nm;
in one embodiment, the particle size of the graphitized filler is 0.5um to 10 um; the pore volume of the internal pores of the natural graphite core is 0.01cm3/g～0.08cm3/g；
In one embodiment, the content of the graphitized filler filled in the internal pores of the natural graphite core is 20 to 80 percent based on 100 percent of the mass of the graphitized filler.
In a second aspect, the present invention provides a method for preparing a graphite anode material as in the first aspect, the method comprising the steps of:
mixing natural graphite with a filler to obtain a mixture;
crushing the mixture to obtain graphite powder; and
graphitizing the graphite powder under a protective atmosphere to obtain the graphite cathode material.
According to the preparation method provided by the invention, the natural graphite and the filler are uniformly mixed, then the solid filler is embedded in the natural graphite particles in the process of crushing and spheroidizing, and then the filler embedded in the natural graphite particles can eliminate the defects in the natural graphite particles through graphitization treatment to form a densified structure, so that the performance of the product is improved.
In the method provided by the invention, after the natural graphite and the filler are uniformly mixed, in the process of crushing and spheroidizing, the filler is embedded into the graphite and is coated on the outer surface of the natural graphite. The internal compact and external coating structure is formed after heat treatment, so that the internal defects of the natural graphite are eliminated, the problem of selectivity of the natural graphite and electrolyte is thoroughly solved, and the cycle performance of the natural graphite is improved.
In one embodiment, the natural graphite is natural flake graphite.
In one embodiment, the natural graphite has a median particle diameter (D50) of 10 μm to 150 μm.
In one embodiment, the filler comprises pitch and/or resin.
In one embodiment, the bitumen comprises at least one of petroleum bitumen, coal bitumen, mesophase bitumen, and upgraded bitumen;
in one embodiment, the pitch has a median particle size of 1 μm to 10 μm.
In one embodiment, the resin comprises a phenolic resin and/or an epoxy resin.
In one embodiment, the mass ratio of the natural graphite to the filler is 10 (0.5-3).
In one embodiment, the comminuting is while spheronizing.
In one embodiment, the median particle diameter of the graphite powder is 8-25 μm.
In one embodiment, the graphite powder is spherical graphite powder.
In one embodiment, the protective atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;
in one embodiment, the graphitization treatment temperature is 2000-3300 ℃ and the time is 10-72 h.
In one embodiment, the preparation method further comprises: and scattering and screening the product obtained by the graphitization treatment.
In one embodiment, the method comprises the steps of:
physically mixing natural crystalline flake graphite with the median particle size of 10-150 mu m with asphalt with the median particle size of 1-10 mu m according to the mass ratio of 10 (0.5-3) to obtain a mixture;
crushing and spheroidizing the mixture to obtain spherical graphite powder with the median particle size of 8-25 mu m; and
graphitizing the spherical graphite powder for 10-72 h at 2000-3300 ℃ in a protective atmosphere to obtain the graphite cathode material.
In a third aspect, the invention provides a lithium ion battery comprising the graphite negative electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method provided by the invention simultaneously performs the spheroidization of the natural graphite, the mixed coating of the spherical graphite and the filler and the filling of the filler in the internal gap of the spherical graphite, reduces the turnover and residual loss of materials, and has simple process and high production efficiency; the natural graphite and the filler are mixed together for crushing-spheroidizing, so that the defect that a large number of gaps exist in the crushing-spheroidizing of single flake graphite can be overcome, an internal compact structure is formed, and the product has the advantages of small expansion, good circulation and excellent comprehensive performance.
(2) The graphite cathode material provided by the invention has the advantages of small expansion, good circulation and excellent comprehensive performance.
Drawings
Fig. 1 is a sectional test chart of a scanning electron microscope of the graphite negative electrode material prepared in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
An embodiment provides a graphite anode material, including:
the natural graphite core is provided with pores inside;
the carbon coating layer is formed on the surface of the natural graphite core;
the graphitized filler is filled in the internal pores of the natural graphite core; and the graphitizing filler also forms the carbon coating.
The filling agent is filled in the hole defect inside the graphite core of the graphite cathode material provided by the embodiment, the graphitized filling agent forms a carbon coating layer on the surface of the natural graphite core at the same time, the natural graphite core is internally compact, the external coating structure eliminates the internal defect of the natural graphite, the material is small in expansion, good in circulation and excellent in comprehensive performance, the problem of selectivity of the natural graphite and an electrolyte is thoroughly solved, and the cycle performance of the natural graphite is further improved.
In some embodiments, the natural graphite inner core has a median particle size of 8 to 25 μm, such as 8 μm, 10 μm, 15 μm, 20 μm, or 25 μm, and the like.
In some embodiments, the graphitized filler comprises at least one of pitch and resin.
In some embodiments, the coating has a thickness of 10-100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100nm, and the like.
In some embodiments, the graphitized filler has a particle size of 0.5um to 10 um; the pore volume of the internal pores of the natural graphite core is 0.01cm3/g～0.08cm3(ii)/g; the parameter setting enables the graphitized filler to completely fill the internal pores of the natural graphite to form an internal compact structure.
In some embodiments, the graphitized filler is filled in the internal pores of the natural graphite core in an amount of 20% to 80% by mass of the graphitized filler as 100%. If the content of the graphitized filler is too small, the internal pores of the graphite cannot be completely filled; too low a content of the graphitized filler may result in negative effects such as a low material capacity and a low compaction.
Another embodiment provides a method of preparing a graphite anode material, the method including the steps of:
mixing natural graphite with a filler to obtain a mixture;
crushing the mixture to obtain graphite powder; and
graphitizing the graphite powder under a protective atmosphere to obtain the graphite cathode material.
According to the preparation method provided by the invention, the natural graphite and the filler are uniformly mixed as much as possible, then the solid filler is embedded in the natural graphite particles in the process of crushing and spheroidizing, and then the filler embedded in the natural graphite particles can eliminate the defects in the natural graphite particles through graphitization treatment, so that a densified structure is formed, and the performance of the product is further improved.
In the method provided by the invention, after the natural graphite and the filler are uniformly mixed, in the process of crushing and spheroidizing, the filler is embedded into the graphite and is coated on the outer surface of the natural graphite. The internal compact and external coating structure is formed after heat treatment, so that the internal defects of the natural graphite are eliminated, the problem of selectivity of the natural graphite and electrolyte is thoroughly solved, and the cycle performance of the natural graphite is improved.
The preparation method provided by the invention simultaneously performs the spheroidization of the natural graphite, the mixed coating of the spherical graphite and the filler and the filling of the filler in the internal gap of the spherical graphite, reduces the turnover and residual loss of materials, and has simple process and high production efficiency; the natural graphite and the filler are mixed together for crushing-spheroidizing, so that the defect that a large number of gaps exist in the crushing-spheroidizing of single flake graphite can be overcome, an internal compact structure is formed, the material expansion is small, the circulation is good, and the comprehensive performance is excellent.
In some embodiments, the natural graphite is natural flake graphite.
In some embodiments, the natural graphite has a median particle diameter D50 of 10 μm to 150 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, or 150 μm, but is not limited to the recited values, and other values not recited within this range of values are equally applicable.
In some embodiments, the filler comprises pitch and/or resin. The two fillers are adopted because the asphalt and the resin are solid powder at normal temperature, and can enter the internal pores of the spherical graphite in the process of grinding the spherical graphite, and are melted into liquid state in the process of high-temperature graphitization and then solidified into solid state, so that the internal defects of the natural graphite can be compactly eliminated, and meanwhile, a carbon structure coating layer is formed on the outer surface to prevent the natural graphite from directly contacting with electrolyte, thereby improving the performance of products.
In some embodiments, the bitumen comprises at least one of petroleum bitumen, coal bitumen, mesophase bitumen, and upgraded bitumen. Typical but non-limiting combinations are: a combination of petroleum pitch and coal pitch, a combination of coal pitch and mesophase pitch, a combination of mesophase pitch and modified pitch, and the like.
In some embodiments, the pitch has a median particle diameter D50 of 1 μm to 10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, but is not limited to the recited values, and other values not recited within this range are equally applicable.
In some embodiments, the resin comprises a phenolic resin and/or an epoxy resin.
In some embodiments, the mass ratio of the natural graphite to the filler is 10 (0.5-3), such as 10:0.5, 10:0.8, 10:1, 10:1.2, 10:1.4, 10:1.6, 10:1.8, 10:2, 10:2.2, 10:2.4, 10:2.6, 10:2.8, or 10:3, but not limited to the recited values, and other values within the range are equally applicable.
In the invention, if the mass ratio of the natural graphite to the filler is too large (i.e. the filler is too little), the internal pores of the graphite cannot be completely filled; if the mass ratio of the natural graphite to the filler is too small (i.e., the filler is too much), negative effects such as a low material capacity and a low compaction result.
In some embodiments, the comminuting is comminuting while spheronizing.
In some embodiments, the spheronization is treated with a mechanical mill.
In some embodiments, the graphite powder has a median particle diameter D50 of 8 μm to 25 μm, such as 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, or 25 μm, but is not limited to the recited values, and other values not recited in this range are equally applicable.
In some embodiments, if the median particle size of the graphite powder obtained after the pulverization and the spheroidization is too large, the Dmax of the material is too large, and the diaphragm is punctured in the battery preparation process, so that the battery short circuit occurs and the safety performance of the battery is affected; if the median particle diameter of the graphite powder obtained after the pulverization and spheroidization is too small, the yield of the spherical graphite is low, and the cost is high.
In some embodiments, the graphite powder is a spherical graphite powder.
In some embodiments, the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere;
in some embodiments, the graphitization treatment temperature is 2000 ℃ to 3300 ℃, such as 2000 ℃, 2100 ℃, 2200 ℃, 2300 ℃, 2400 ℃, 2500 ℃, 2600 ℃, 2700 ℃, 2800 ℃, 2900 ℃, 3000 ℃, 3100 ℃, 3200 ℃, or 3300 ℃, but is not limited to the recited values, and other values not recited within this range are equally applicable.
In some embodiments, the graphitization treatment time is 10h to 72h, such as 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, or 72h, but is not limited to the recited values, and other non-recited values within this range are equally applicable.
In some embodiments, the method of making further comprises: and scattering and screening the product obtained by the graphitization treatment.
An embodiment provides a method for preparing the lithium nickel cobalt complex oxide, including the steps of:
physically mixing natural crystalline flake graphite with the median particle size of 10-150 mu m with asphalt with the median particle size of 1-10 mu m according to the mass ratio of 10 (0.5-3) to obtain a mixture;
crushing and spheroidizing the mixture to obtain spherical graphite powder with the median particle size of 8-25 mu m; and
graphitizing the spherical graphite powder for 10-72 h at 2000-3300 ℃ in a protective atmosphere to obtain the graphite cathode material.
The further optimized technical scheme is that the flake graphite and the asphalt are mixed together to be crushed and spheroidized. In the crushing-spheroidizing process, the crystalline flake graphite is curled and folded, and the asphalt is embedded into the spherical graphite and is simultaneously coated on the outer surface layer of the spherical graphite. The flake graphite and the asphalt are crushed and spheroidized together, so that the defect that a large number of gaps exist in the crushed and spheroidized single flake graphite can be overcome, and the outer surface layer of the spherical graphite is uniformly coated with the asphalt. The expansion rate of the natural graphite is reduced and the cycle performance is improved.
An embodiment provides a lithium ion battery comprising the graphite negative electrode material.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (D50 is 70 mu m) and petroleum asphalt (the softening point is 120 ℃ and the D50 is 5 mu m) as raw materials, mixing the raw materials and the petroleum asphalt in a mass ratio of 10:1, adding the raw materials into a mechanical crusher together to perform crushing-spheroidizing treatment after mechanical and physical mixing, wherein the spherical graphite D50 is 8 mu m, and graphitizing the prepared spherical graphite material for 10 hours at 3200 ℃ in a nitrogen atmosphere. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The natural graphite core provided by the embodiment comprises a natural graphite core and a carbon coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is formed by graphitizing asphalt. The graphite core has a D50 value of 8 μm and the carbon coating layer has a thickness of 40 nm.
Fig. 1 is a sectional test chart of a scanning electron microscope of the graphite negative electrode material prepared in this example, from which it can be seen that the interior of the natural spherical graphite is completely filled and compacted with asphalt, and the outer surface layer forms a uniform coating layer.
Example 2
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (D50 is 70 mu m) and petroleum asphalt (the softening point is 180 ℃, D50 is 3 mu m) as raw materials, mixing the raw materials and the petroleum asphalt in a mass ratio of 10:1, adding the raw materials into a mechanical crusher together for crushing and spheroidizing after mechanical and physical mixing, wherein the spherical graphite D50 is 8 mu m, and graphitizing the prepared spherical graphite material at 3000 ℃ for 24 hours. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The graphite core comprises a natural graphite core and a carbon coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is formed by graphitizing asphalt. The D50 of the natural graphite core is 8 μm, and the thickness of the carbon coating layer is 60 nm.
Example 3
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (with the average particle size D50 of 120 mu m) and petroleum asphalt (with the softening point of 250 ℃ and the softening point of D50 of 2 mu m) as raw materials, mixing the raw materials and the petroleum asphalt in a mass ratio of 10:2, adding the raw materials into a mechanical crusher together for crushing and spheroidizing, wherein the spherical graphite D50 is 17 mu m, and graphitizing the prepared spherical graphite material at 2800 ℃ for 36 hours. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The natural graphite core comprises a natural graphite core and a carbon coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in pores inside the natural graphite core, the natural graphite core has no gap defects, and the carbon coating layer is formed by graphitizing asphalt. The D50 of the natural graphite core is 17 μm, and the thickness of the carbon coating layer is 80 nm.
Example 4
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (with the average particle size D50 of 120 mu m) and petroleum asphalt (with the softening point of 120 ℃ and the softening point of D50 of 5 mu m) as raw materials, mixing the natural crystalline flake graphite and the petroleum asphalt in a mass ratio of 10:2, adding the raw materials into a mechanical crusher together for crushing and spheroidizing, wherein the spherical graphite D50 is 17 mu m, and graphitizing the prepared spherical graphite material at 3200 ℃ for 10 hours. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The natural graphite core comprises a natural graphite core and a coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is formed by graphitizing asphalt. The graphite core has a D50 of 17 μm and the carbon coating layer has a thickness of 80 nm.
Example 5
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (with the average particle size D50 of 150 mu m) and petroleum asphalt (with the softening point of 180 ℃ and the softening point of D50 of 3 mu m) as raw materials, mixing the raw materials in a mass ratio of 10:3, adding the raw materials into a mechanical crusher together for crushing and spheroidizing, wherein the spherical graphite D50 is 23 mu m, and graphitizing the prepared spherical graphite material at 3000 ℃ for 24 hours. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The natural graphite core comprises a natural graphite core and a coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is formed by graphitizing asphalt. The D50 of the natural graphite core is 23 μm, and the thickness of the carbon coating layer is 100 nm.
Example 6
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (with the average particle size D50 of 150 mu m) and petroleum asphalt (with the softening point of 250 ℃ and the softening point of D50 of 2 mu m) as raw materials, mixing the raw materials in a mass ratio of 10:3, adding the raw materials into a mechanical crusher together for crushing and spheroidizing, wherein the spherical graphite D50 is 23 mu m, and graphitizing the prepared spherical graphite material at 2800 ℃ for 36 hours. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The natural graphite core comprises a natural graphite core and a coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is formed by graphitizing asphalt. The D50 of the natural graphite core is 23 μm, and the thickness of the carbon coating layer is 100 nm.
Example 7
This example prepares a graphite negative electrode material as follows:
the method comprises the steps of taking natural crystalline flake graphite (with the average particle size D50 of 10 mu m) and coal tar pitch (with the softening point of 250 ℃ and the softening point of D50 of 2 mu m) as raw materials, mixing the raw materials in a mass ratio of 10:0.5, adding the raw materials into a mechanical crusher together for crushing and spheroidizing, wherein the spherical graphite D50 is 8 mu m, and graphitizing the prepared spherical graphite material at 3300 ℃ for 10 hours. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The graphite core comprises a natural graphite core and a carbon coating layer coated on the surface of the natural graphite core, wherein graphitized asphalt is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is a carbon structure layer formed by graphitizing asphalt. The D50 of the natural graphite core is 8 μm, and the thickness of the carbon coating layer is 10 nm.
Example 8
The method comprises the steps of taking natural crystalline flake graphite (with the average particle size D50 of 100 mu m) and phenolic resin as raw materials, taking the natural crystalline flake graphite and the phenolic resin in a mass ratio of 10:2, mechanically and physically mixing the raw materials, adding the mixed raw materials into a mechanical crusher together for crushing-spheroidizing treatment, taking the spherical graphite D50 as 25 mu m, and graphitizing the prepared spherical graphite material for 72 hours at 2000 ℃. And finally, sieving the material, and collecting the sieved material to obtain a finished graphite cathode material.
The graphite core comprises a natural graphite core and a carbon coating layer coated on the surface of the natural graphite core, wherein graphitized phenolic resin is filled in a pore defect inside the natural graphite core, the natural graphite core has no gap defect, and the carbon coating layer is a carbon structure layer formed by graphitizing the phenolic resin. The D50 of the natural graphite core is 25 μm, and the thickness of the carbon coating layer is 80 nm.
Comparative example 1
Taking natural crystalline flake graphite (the average particle size D50 is 70 mu m) as a raw material, adding the raw material into a mechanical crusher for crushing and spheroidizing treatment, wherein the spherical graphite D50 is 8 mu m, mixing the prepared spherical graphite material with petroleum asphalt (the softening point is 120 ℃, and the D50 is 5 mu m), the mass ratio of the spherical graphite material to the petroleum asphalt is 10:1, and graphitizing the mixed powder for 10 hours at 3200 ℃. And finally, sieving the material, and collecting the sieved material to obtain a finished product of the graphite cathode material (namely, the embodiment is the same as the embodiment 1 except that the material is firstly crushed and then mixed with the asphalt).
The graphite core comprises a graphite core and a coating layer coated on the surface of the graphite core, wherein the inside of the graphite core has no filler in pore defects, and the coating layer is a carbon structural layer formed by the graphitization of asphalt. The graphite core has a D50 value of 8 μm and the coating layer has a thickness of 45 nm.
Comparative example 2
Taking natural crystalline flake graphite (the average particle size D50 is 120 mu m) as a raw material, adding the raw material into a mechanical crusher for crushing and spheroidizing treatment, wherein the spherical graphite D50 is 17 mu m, mixing the prepared spherical graphite material with petroleum asphalt (the softening point is 250 ℃, and the D50 is 2 mu m) according to the mass ratio of 10:2, and graphitizing the mixed powder for 36 hours at 2800 ℃. And finally, sieving the material, and collecting the sieved material to obtain a finished product of the graphite cathode material (namely, the embodiment is the same as the embodiment 3 except that the material is firstly crushed and then mixed with the asphalt).
The graphite core comprises a graphite core and a coating layer coated on the surface of the graphite core, wherein the inside of the graphite core has no filler in pore defects, and the coating layer is a carbon structural layer formed by the graphitization of asphalt. The graphite core had a D50 value of 17 μm and the coating had a thickness of 65 nm.
Comparative example 3
Taking natural crystalline flake graphite (the average particle size D50 is 150 mu m) as a raw material, adding the raw material into a mechanical crusher for crushing and spheroidizing treatment, wherein the spherical graphite D50 is 23 mu m, mixing the prepared spherical graphite material with petroleum asphalt (the softening point is 250 ℃, and the D50 is 2 mu m) according to the mass ratio of 10:3, and graphitizing the mixed powder for 36 hours at 2800 ℃. And finally, sieving the material, and collecting the sieved material to obtain a finished product of the graphite cathode material (namely, the embodiment is the same as the embodiment 6 except that the material is firstly crushed and then mixed with the asphalt).
The graphite core comprises a graphite core and a coating layer coated on the surface of the graphite core, wherein the inside of the graphite core has no filler in pore defects, and the coating layer is a carbon structural layer formed by the graphitization of asphalt. The graphite core has a D50 value of 23 μm and the coating layer has a thickness of 110 nm.
Test method
The graphite negative electrode materials prepared in examples or comparative examples were used as negative electrode active materials, and the ratio of the active material: CMC: and uniformly mixing SBR (styrene butadiene rubber) in a mass ratio of 96.5:1.5:2, coating the mixture on a copper foil current collector, and drying to obtain a negative pole piece for later use.
And (3) carrying out button cell test on the obtained pole piece: the battery is assembled in an argon glove box, a metal lithium sheet is taken as a negative electrode, and the electrolyte is 1mol/L LiPF6+ EC + EMC, the diaphragm is a polyethylene/propylene composite microporous film, the electrochemical performance is carried out on a battery test instrument, the charge-discharge voltage is 0.01-1.5V, the charge-discharge rate is 0.1C, and the first capacity and efficiency obtained by the test are listed inTable 1. The button cell was tested for 50 cycles of expansion at 0.1C charge and discharge in the first week, 0.2C charge and discharge in week 2, and 0.5C charge and discharge in the following.
Testing a finished battery: and mixing the natural graphite-based composite material obtained from the graphite negative electrode material prepared in the embodiment or the comparative example, the conductive agent, the CMC and the SBR according to the mass ratio of 95:1.5:1.5:2, and coating the mixture on a copper foil to obtain a negative electrode piece. LiCoO as positive electrode active material2The conductive agent and the PVDF are uniformly mixed according to the mass ratio of 96.5:2:1.5 and then coated on an aluminum foil to obtain the positive pole piece. The electrolyte is 1mol/L LiPF6+ EC + EMC, the diaphragm is a polyethylene/propylene composite microporous membrane, normal-temperature charging and discharging are carried out at the multiplying power of 1C, the voltage range is 3.0-4.25V, and the cycle performance obtained by testing is listed in Table 1.
TABLE 1
Figure BDA0002675720010000141
Figure BDA0002675720010000151
It can be known from the above examples and comparative examples that the graphite negative electrode materials provided in examples 1 to 8 of the present invention reduce material turnover and residual loss due to the simultaneous implementation of spheroidization of natural graphite, mixed coating of spherical graphite and a filler, and filling of the filler in gaps inside the spherical graphite, and have a simple process and high production efficiency; the natural graphite and the filler are mixed together for crushing-spheroidizing, so that the defect that a large number of gaps exist in the crushing-spheroidizing of single flake graphite can be overcome, an internal compact structure is formed, and the product has the advantages of small expansion, good circulation and excellent comprehensive performance.
Compared with the example 1, the comparative example 2 and the comparative example 3, and the comparative example 3 and the example 6, the natural graphite is firstly spheroidized, then the mixed coating of the spherical graphite and the filler is carried out, and the filler is filled in the internal gaps of the spherical graphite, and the three operations are not carried out simultaneously, so that the filler is simply coated on the surface of the graphite and cannot enter the internal gaps of the graphite, the structure still has defects, the expansion rate of the products of the comparative examples 1-3 is greatly increased compared with the products of the examples, and the cycle performance is greatly reduced.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A graphitic negative electrode material, characterized in that it comprises:
a natural graphite core having pores therein;
the carbon coating layer is formed on the surface of the natural graphite core;
a graphitized filler filled in the internal pores of the natural graphite core; and the graphitizing filler also forms the carbon coating.
2. The graphite anode material according to claim 1, wherein the natural graphite core has a median particle diameter of 8 to 25 μm;
preferably, the filler in the graphitized filler includes at least one of pitch and resin;
preferably, the thickness of the carbon coating layer is 10 nm-100 nm;
the particle size of the graphitized filler is 0.5-10 um; the pore volume of the internal pores of the natural graphite core is 0.01cm3/g～0.08cm3/g；
The content of the graphitized filler filled in the internal pores of the natural graphite core is 20-80% by taking the mass of the graphitized filler as 100%.
3. A preparation method of a graphite negative electrode material is characterized by comprising the following steps:
mixing natural graphite with a filler to obtain a mixture;
crushing the mixture to obtain graphite powder; and
graphitizing the graphite powder under a protective atmosphere to obtain the graphite cathode material.
4. The production method according to claim 3, wherein the natural graphite is natural flake graphite;
preferably, the natural graphite has a median particle diameter of 10 to 150 μm.
5. The production method according to claim 3 or 4, wherein the filler comprises at least one of asphalt and resin;
preferably, the bitumen comprises at least one of petroleum bitumen, coal bitumen, mesophase bitumen and upgraded bitumen;
preferably, the median particle size of the asphalt is 1 to 10 μm;
preferably, the resin comprises a phenolic resin and/or an epoxy resin.
6. The preparation method according to any one of claims 3 to 5, wherein the mass ratio of the natural graphite to the filler is 10 (0.5 to 3);
preferably, the pulverization is pulverization while spheroidization;
preferably, the median particle diameter of the graphite powder is 8-25 μm;
preferably, the graphite powder is spherical graphite powder.
7. The method of any one of claims 3-6, wherein the protective atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;
preferably, the temperature of the graphitization treatment is 2000-3300 ℃, and the time is 10-72 h.
8. The production method according to any one of claims 3 to 7, characterized by further comprising: and scattering and screening the product obtained by the graphitization treatment.
9. The method for preparing according to any one of claims 3 to 8, characterized in that it comprises the steps of:
physically mixing natural crystalline flake graphite with the median particle size of 10-150 mu m with asphalt with the median particle size of 1-10 mu m according to the mass ratio of 10 (0.5-3) to obtain a mixture;
crushing and spheroidizing the mixture to obtain spherical graphite powder with the median particle size of 8-25 mu m; and
graphitizing the spherical graphite powder for 10-72 h at 2000-3300 ℃ in a protective atmosphere to obtain the graphite cathode material.
10. A lithium ion battery comprising the graphite negative electrode material according to claim 1 or 2.
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